The adsorption and dissociation of methanol on pure and K-promoted Pd/SiO2 catalysts were investigated by means of FTIR spectroscopy. Spectra were registered at 213-523 K. Absorption bands due to molecularly adsorbed methanol were detected at 213-253 K, whereas methoxy formation was observed at and above 253 K. It appeared that most of the adsorbed methanol and methoxy species were located on the silica support, and only a very small fraction were bonded to the Pd. However, the presence of palladium induced the decomposition of adsorbed methanol even at 233 K, to give CO multiply coordinated to Pd. and CH3CHO. The formation of adsorbed CH3 species was also detected. Addition of potassium did not change the pathways of methanol dissociation, but led to stabilization of the methoxy and acetaldehyde.